WO2006050638A1 - Procede pour la preparation de spheres creuses et spheres creuses composites avec modele - Google Patents

Procede pour la preparation de spheres creuses et spheres creuses composites avec modele Download PDF

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Publication number
WO2006050638A1
WO2006050638A1 PCT/CN2004/001382 CN2004001382W WO2006050638A1 WO 2006050638 A1 WO2006050638 A1 WO 2006050638A1 CN 2004001382 W CN2004001382 W CN 2004001382W WO 2006050638 A1 WO2006050638 A1 WO 2006050638A1
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solution
hollow sphere
concentration
hollow
polymer
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PCT/CN2004/001382
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English (en)
Chinese (zh)
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Zhenzhong Yang
Mu Yang
Jin Ma
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Institute Of Chemistry, Chinese Academy Of Science
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Publication of WO2006050638A1 publication Critical patent/WO2006050638A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/02—Making microcapsules or microballoons

Definitions

  • the invention belongs to the field of hollow structural materials, and particularly relates to a method for preparing inorganic materials, metal, organic hollow spheres and composite structural hollow spheres by using polymer hollow spheres as a template. Background technique
  • the hollow structure sphere is a functional material with special structure.
  • the hollow sphere has great application prospects in the fields of catalysis, drug delivery, artificial cells, lightweight fillers, insulating materials, low dielectric materials, photonic crystals and the like.
  • the preparation of such materials by core-shell structured colloidal particles is a common method.
  • a shell of another (or several) substances is coated or reacted on the surface of one particle to impart new properties to the particle.
  • the shell material can change the surface charge of the colloidal particles, the surface reaction characteristics, and enhance its stability and dispersibility.
  • charged, magnetic, catalytic, optically active, and electrically conductive substances may be introduced on the surface of the colloidal particles as needed to impart functionality to the particles.
  • the method for preparing the core-shell structure mainly includes the following two aspects: (1) surface reaction; (2) surface deposition.
  • American Matijevi0 et al. prepared a core-shell colloidal particle of polydivinylbenzene coated inorganic material by adding a dicobenzene and a free radical initiator to the surface of the inorganic particle (HT Oyama, R. Sprycha, A. Zelenev, E. Mati jevic, "Coating of Uniform Inorganic Particles with Polymers", J. Colloid Polym. Sci. 1993, 160, 298-303; R. Sprycha, HT Oyama, A.
  • Layer adsorption of polyelectrolytes is a very effective method for preparing core-shell structure colloidal particles.
  • the polyelectrolyte-coated colloidal particles can be prepared by adsorbing the oppositely charged polyelectrolyte layer to the surface of the colloidal particles and repeating it a plurality of times.
  • Germany Caruso et al. used monomeric polystyrene colloidal particles as a template to prepare colloidal particles coated with polyvinyl ammonium chloride and polystyrene b: sodium sulfonate by layer-by-layer electrostatic self-assembly. 5 nm ⁇ The average diameter of the colloidal particles increased by about 1. 5 nm.
  • the thickness of the polymer layer can be finely adjusted according to the number of adsorbed layers; colloidal particles of different sizes and shapes can be used as templates for polymerization
  • the layer assembly of the electrolyte The disadvantages are: the residual polyelectrolyte in the system must be removed by repeated centrifugation; the polymer layer of a certain thickness must undergo multiple self-assembly; the uncharged polymer cannot be assembled. Yang Zhenzhong et al.
  • the advantage of this method is to control sulfonation.
  • the thickness of the layer can simultaneously adjust the size of the cavity and the thickness of the shell, and the sulfonated layer provides a hydrophilic layer.
  • the hollow spheres prepared by the template method are obtained by using colloidal particles as a template, and the core-shell composite particles are obtained by surface deposition reaction or layer-by-layer alternating adsorption, and hollow spheres are obtained after enucleation. Summary of the invention
  • One of the objects of the present invention is to provide a method for preparing hollow spheres of inorganic, metal and/or organic composite structures using polymeric hollow spheres as a template.
  • a further object of the present invention is to provide a method for preparing hollow spheres of inorganic, metal and/or organic composite structures by a composite process.
  • Still another object of the present invention is to provide the use of hollow spheres and composite structural hollow spheres.
  • the invention utilizes a polymer hollow sphere as a template, uses a shell as a forced interface, a cavity as a raw material warehouse of a reaction component, and another reaction component is placed outside the sphere, and a hollow sphere or a composite structure thereof is prepared by the reaction.
  • the invention prepares a series of hollow structure colloidal particles by using a polymer hollow sphere as a template.
  • Various forms of composite hollow spheres were prepared by sol-gel, sedimentation reaction, redox chemistry or polymerization.
  • the reaction rate is controlled by selecting the reactants, and the morphology of the composite hollow sphere can be controlled by adjusting the feeding mode, the concentration of the reactants, and the reaction conditions.
  • High temperature sintering or solvent selective extraction removes the template polymer to obtain inorganic, metal or organic hollow spheres.
  • the invention uses a polymer hollow sphere as a template to prepare hollow spheres or composites of inorganic substances, metals and organic substances.
  • Inorganic hollow sphere or hollow sphere composite comprising: a metal oxide or hydroxide composite hollow spheres or hollow spheres, such as Ti0 2, Si0 2, Sn0 2 , Zr0 2, A1 2 0 3, V 2 0 5, Zn0 , W0 3 , Mo0 3 , Al (0H) 3 or M g (0H) 2 ; hollow spheres or composite hollow spheres of biomineralized materials, such as CaC0 3 , Ca l0 (P0 4 ) e (0H) 2 , BaS0 4 Or CaS0 4; hollow spheres or composite hollow spheres of semiconductor materials, such as CdS, ZnS, PbS, CuS, CoS, FeS, CdTe, CdSe or ZnSe; hollow spheres or composite hollow spheres of magnetic compounds, such as
  • a hollow sphere of a metal or a composite hollow sphere such as a hollow sphere of a Au, Ag, yttrium, Pd, Pb, Ni, Co, Cu or Fe or a composite hollow sphere.
  • Hollow spheres or composite hollow spheres of organic matter include: hollow spheres or composite hollow spheres of conductive polymers, such as polyaniline, polypyrrole, polythiophene or polyparaphenylene acetylene and derivatives thereof; hollow spheres or composite hollows of sensitive gels
  • a ball such as poly-N-isopropylacrylamide, polyacrylic acid or polymethacrylic acid.
  • Swelling polymerization can be used to prepare high performance polymer hollow spheres or composite hollow spheres, such as crosslinked polystyrene, polyurethane, polyacrylate, phenolic resin, unsaturated polyester, epoxy resin, polyimide, polyether Ketone or polyether sulfones.
  • the method for preparing a hollow sphere and a composite hollow sphere by using a template adopts a commercially available or self-made polymer hollow sphere as a template (diameter is 0.02 ⁇ 4 ⁇ ! ⁇ 10 ⁇ , and the cavity volume is 10 to 95% of the entire microsphere).
  • the polymer hollow spherical shell is composed of two layers of inner and outer materials, the inner layer is a hydrophilic polymer, the outer layer is a lipophilic polymer skeleton, and a hydrophilic channel connects the cavity and the outer environment of the particle.
  • Steps for preparing the growth material in the inner layer of the polymer hollow sphere template shell :
  • the reactant is divided into two reaction components, and there is no reaction between the raw materials in each component.
  • the polymer hollow sphere shell is used as a forced interface, and the cavity is used as a reaction group.
  • another reaction component is placed outside the ball, and a composite hollow sphere of the polymer hollow sphere inner layer growth material can be prepared by the reaction.
  • the resulting polymer hollow sphere containing the inorganic precursor solution is then added to the aqueous solution of the reaction component with stirring.
  • the concentration of the template particles in the reaction solution is maintained at 0. lwt% ⁇ 40. Owt%, the reaction temperature is 0 ° C ⁇ 100 ° C, the reaction time is 0. 5 ⁇ 24 hours or so, the reaction is completed, centrifugal cleaning, the polymer is obtained
  • the chemical solution containing the aqueous solution of the reaction vessel is infiltrated into the polymer hollow sphere template particle cavity, and then the obtained polymer hollow sphere containing the reaction component aqueous solution is added to a concentration of 10. 0wt% ⁇ 60.
  • the concentration of the template particles in the reaction solution is maintained at 0. lwt% ⁇ 40. 0wt%, the reaction temperature is 0 ° C ⁇ 100 ° C, the reaction time is 0. 5 ⁇ 24 hours, the reaction is completed, centrifugal cleaning
  • a composite hollow sphere in which an inorganic substance is grown in the inner layer of the polymer hollow spherical shell is also obtained.
  • the inner layer product of the prepared inorganic composite hollow sphere can be from a single dispersed nanoparticle to a nanoparticle network until Forming a dense shell of different thicknesses. or Lwt% ⁇ 40. Owt%, so that the polymer spheroidal slabs are immersed in a 0. lwt% ⁇ 40.
  • the metal ion salt solution penetrates into the cavity of the polymer hollow sphere template, and after reaching equilibrium, the solution which has not penetrated into the cavity of the polymer hollow sphere template is centrifuged and washed away. 0 ⁇ % ⁇
  • the polymer hollow ball containing the metal ion salt solution was then added to 0. 01wt% ⁇ 60.
  • a composite hollow sphere of metal is grown in the inner layer of the hollow spherical shell.
  • the resulting inner layer product of the metal composite hollow sphere can be from a single dispersed nanoparticle to a nanoparticle network until a dense shell of different thickness is formed.
  • the polymer hollow sphere template particles were soaked at a concentration of 0. 01wt ° /. ⁇ 0. 0wt% of the polymer monomer solution, the template particles in the solution to maintain a concentration of 0. lwt% ⁇ 40. 0wt ° / » the polymer monomer solution penetrates into the cavity of the polymer hollow sphere template, After the equilibrium is reached, the solution that has not penetrated into the cavity of the hollow polymer template is centrifuged and washed away. The polymer hollow cell containing the polymer monomer solution is then added to 0. 01wt% ⁇ 30. 0% of the initiator solution in a stirred solution.
  • the reaction time is 0. 5 ⁇ 24 hours or so, the reaction time is 0. 5 ⁇ 24 hours or so, the reaction time is 0. 5 ⁇ 24 hours, the reaction time is 0. 5 ⁇ 24 hours, the reaction time is 0. After completion, centrifugal cleaning, that is, a composite hollow sphere in which organic matter is grown in the inner layer of the polymer hollow spherical
  • the singularity of the singularity of the singularity of the singularity of the singularity of the singularity of the singularity of the singularity of the present invention is increased to 300 ⁇ 700 ° C (preferably 450 ° C) and the ignition is about 0.2 to 3 hours, respectively, to obtain inorganic or metal hollow spheres;
  • the polymer template obtained by the step (1.1), the step (1.2), the step (1.3), and the hollow sphere compounded with the inorganic substance, the metal or the organic substance are respectively extracted by using a selective solvent to remove the template polymerization. Objects, respectively, get inorganic, metal or organic hollow spheres.
  • Step (1. 1), step (1.2), and step (1. 3) may be repeated a plurality of times before proceeding to step (2).
  • Step (1.1), step (1.2), and step (1.3) respectively the composite hollow spheres are used as templates, and steps (1.1), steps (1.2), and steps (1. 3), performing a cyclic reaction, when two or more cycles of the reaction to form the same substance, the shell thickness of the composite hollow sphere can be increased, that is, the thickness of the hollow spherical shell can be controlled by controlling the concentration of the reactants and the number of cycles of the reaction; or
  • the composite hollow sphere obtained in the step (1.2) or the step (1.3) is used as a template particle of the step (1.1) to carry out a cyclic reaction; or
  • the composite hollow sphere obtained in the step (1.1) or the step (1.3) is used as a template particle of the step (1.2) to carry out a cyclic reaction; or
  • the composite hollow sphere obtained in the step (1.1) or the step (1.2) is used as a template particle of the step (1.3) to carry out a cyclic reaction.
  • composite hollow spheres of various materials can be obtained.
  • the polymer template first forms titanium dioxide in the inner layer of the shell, and then forms silica in the inner layer of the shell to obtain a polymer.
  • a composite hollow sphere of template and titanium dioxide and silicon dioxide; or a polymer template first generates ferroferric oxide in the inner layer of the shell, and then forms polyaniline in the inner layer of the shell to obtain a composite of the polymer template and triiron tetroxide and polyaniline. Hollow ball.
  • the composite hollow sphere with the surface of the burr-like substance can be obtained, and the polymer hollow sphere template
  • the inner layer of the shell creates a continuous material whose hydrophilic channels are reshaped, expanded, and even extended out of the sphere.
  • the aqueous solution of the reaction component is infiltrated into the cavity of the hollow polymer template of the polymer to reach a concentration of the polymer hollow sphere template particles in the solution After the equilibration, the solution that has not penetrated into the cavity of the hollow polymer template is centrifuged and washed away. The weight of the aqueous solution of the inorganic precursor is maintained at 0. 01wt ° / by the continuous replenishment.
  • the reaction time is 0. 5 ⁇ 24 hours, the reaction time is 0. 5 ⁇ 24 hours or so, the reaction time is 0. lwt% ⁇ 40. 0wt%, reaction temperature 0O ⁇ 100 ° C, reaction time 0.
  • the reducing agent solution is infiltrated into the polymer.
  • the weight of the template is kept in the solution.
  • the cavity of the hollow sphere template is centrifuged to remove the solution that has not penetrated into the cavity of the polymer hollow sphere template. 01wt°/ ⁇
  • the polymer ionic salt was added to the metal ion salt solution with agitation. 5 ⁇ 24 ⁇
  • the reaction time is 0. lwt% ⁇ 40. 0wt%, reaction temperature 0 ° C ⁇ 100 ° C, reaction time 0. 5 ⁇ 24 hours or so , the reaction is completed, and the centrifugal cleaning is performed to obtain the surface band.
  • the polymer template of the ranunculus-like material and the hollow sphere of the metal composite, the hydrophilic channel of which is shaped, expanded or even protruded from the sphere, and the inner layer of the shell generates a continuous material; or
  • the polymer hollow sphere template particles were immersed in the reaction composition concentration of 0. 01wt% ⁇ 30. 0wt°/ ⁇
  • the template particles are kept at a concentration of 0. lwt% ⁇ 40. (kt%, the initiator solution is infiltrated into the cavity of the polymer hollow sphere template, and after reaching equilibrium, the polymer hollow sphere template is not infiltrated.
  • the weight of the polymer monomer is maintained at 0. 01wt% ⁇ 10.
  • the concentration of the template particles in the reaction solution is maintained at 0. lwt% ⁇ 40. (kt%, reaction temperature 0°C ⁇ 100°C, reaction time) 0.
  • the polymer template obtained in the step (1) and the inorganic material, metal composite hollow spheres are placed in a sintering furnace, and air is passed, and the temperature is raised to a temperature of 0.1 to 10 ° C / minute to 300 ⁇ 700 ° C (preferably 450 ⁇ ) burning 0. 2 ⁇ 3 hours, obtaining an inorganic or metallic hollow sphere with a burr surface; or
  • the hollow template obtained by mixing the polymer template obtained in the step (1) with an inorganic material, a metal or an organic substance is extracted with a selective solvent to remove the template polymer to obtain a surface-burred inorganic material, metal or organic hollow sphere.
  • the hollow sphere of the burr-type hollow sphere is formed by growing a material in the inner layer of the casing, and the burr is formed by the growth and expansion of the material in the hydrophilic passage.
  • the polymer hollow sphere is used as a template, which is dispersed in a solution, and two reaction components of the inorganic substance, the metal or the organic substance are added to the solution to control a certain concentration, and the reaction product can be deposited and grown on the outer surface of the hollow shell of the polymer. And no reaction product particles are formed in the solution.
  • the final concentration is 0. lwt% ⁇ 50wt%
  • the concentration of the template particles is 0. lwt ° /. ⁇ 40wt%
  • reaction temperature 0 ° C ⁇ 100 ° C reaction time 0. 5 ⁇ 24 hours
  • the reaction product is deposited on the outer surface of the polymer hollow spherical shell to form a continuous shell.
  • the mixture is centrifuged to obtain a composite hollow sphere which grows inorganic substances on the outer surface of the hollow shell of the polymer; the polymer template is removed to obtain an inorganic hollow sphere; or
  • the weight of the metal ion salt is 0.11% by weight to 30% by weight, and the reducing agent concentration is 0.11% by weight to 30% by weight.
  • the concentration of the template particles is 0. lwt% ⁇ 40wt%
  • the reaction temperature is 0 ° C ⁇ : L00 ° C
  • the reaction time is 0. 5 ⁇ 24 hours
  • the reaction product is deposited on the outer surface of the hollow shell of the polymer to form a continuous shell Floor.
  • centrifugal cleaning is performed to obtain a composite hollow sphere which grows metal on the outer surface of the hollow shell of the polymer; the polymer template is removed to obtain a hollow metal sphere; or
  • the reaction temperature is 0°.
  • the concentration of the template particles is 0. lwt% ⁇ 40wt%
  • the reaction temperature is 0°
  • the concentration of the initiator is 0. 01wt% ⁇ 20wt%
  • the concentration of the template particles is 0. lwt% ⁇ 40wt%
  • the reaction temperature is 0°. C ⁇ 100 ° C, reaction time 0. 5 ⁇ 24 hours
  • the reaction product is deposited on the outer surface of the hollow shell of the polymer to form a continuous shell; after the reaction is completed, centrifugal cleaning, the outer surface of the hollow shell of the polymer is obtained.
  • the hollow sphere of the polymer and the organic compound; the template polymer is removed to obtain an organic hollow sphere.
  • the reactant is divided into two reaction components, and there is no reaction between the raw materials in each component.
  • the polymer hollow sphere shell is used as a forced interface, and the cavity is used as a reaction group.
  • another reaction component is placed outside the ball, and a composite hollow sphere of the inner growth material of the polymer hollow spherical shell is prepared by the reaction.
  • the resulting polymer hollow sphere containing the inorganic precursor solution is then added to the aqueous solution of the reaction component with stirring.
  • the concentration of the template particles in the reaction solution is maintained at 0. lwt% ⁇ 40. 0wt%, the reaction temperature is 0 ° C ⁇ 100 ° C, the reaction time is 0. 5 ⁇ 24 hours or so, the reaction is completed, centrifugal cleaning, the polymer is obtained
  • the inorganic material of the present invention is added to the inorganic material having a concentration of 10. 0 wt% to 60. 03 ⁇ 4 ⁇ %.
  • the concentration of the template particles in the reaction solution is maintained at 0. rt% ⁇ 40. 0wt%, reaction temperature 0 ° C; ⁇ 100 ° C, reaction time 0. 5 ⁇ 24 hours, the reaction is completed, centrifugal cleaning, the same polymerization
  • the template particles are kept at a concentration of 0. lwt e /, in the solution of the metal ion salt solution. ⁇ 40. 0wt%, the metal ion salt solution is infiltrated into the cavity of the polymer hollow sphere template, and after reaching equilibrium, the solution not penetrating into the cavity of the polymer hollow sphere template is centrifuged and washed away. 0 ⁇ % ⁇ The polymer hollow sphere containing the metal ion salt solution was then added to 0. 01wt% ⁇ 60. 0 ⁇ % of the reducing agent solution. The concentration of the template particles in the reaction solution is maintained at 0. lwt% ⁇ 40.
  • the reaction temperature is 0 ° C ⁇ 100 ° C
  • the reaction time is 0. 5 ⁇ 24 hours
  • the reaction is completed, centrifuged, clear, that is A composite hollow sphere of metal is grown in the inner layer of the polymer hollow spherical shell.
  • 0wt% initiator solution is infiltrated into the hollow cavity template particle cavity of the polymer, and then the obtained polymer hollow sphere containing the initiator solution is added to the concentration of 5 ⁇ % ⁇ 4 under stirring.
  • the inert gas is introduced into the reaction vessel, and the concentration of the template particles in the reaction solution is kept at 0. lwt% ⁇ 40wt%, the reaction temperature is 0°C ⁇ 100°C, and the reaction time is 0. 5 ⁇ 24 hours, the reaction is completed, and the mixture is centrifuged to obtain a composite hollow sphere in which the organic layer of the polymer hollow sphere is grown.
  • the outer surface of the spherical shell can obtain a multi-layer composite hollow sphere which grows materials on both the outer surface and the inner layer of the polymer hollow spherical shell, and removes the polymer template to obtain a double-layer hollow sphere, that is, the hollow sphere contains a hollow sphere therein.
  • the hollow sphere can move within the outer hollow sphere.
  • the final concentration of the inorganic precursor in the reaction liquid is 0. 01wt%
  • the final concentration of the inorganic precursor in the reaction liquid is 0. 01wt% Lwt°/ ⁇
  • the final concentration of the aqueous solution of the reaction component is 0. lwt ° /. ⁇ 50wt%
  • the concentration of the template particles is 0. lwt% ⁇ 40wt%
  • the reaction temperature is 0 ° C ⁇ 100 V
  • the reaction time is 0. 5 ⁇ 24 hours
  • the reaction product is deposited on the outer surface of the polymer hollow spherical shell, forming a continuous Shell layer.
  • a composite hollow sphere in which inorganic substances are grown on the outer surface and the inner layer of the hollow shell of the polymer is obtained.
  • the polymer template is removed to obtain a two-layer inorganic hollow sphere, that is, the hollow sphere contains a hollow sphere, and the hollow sphere obtained in the two-layer structure can move in the outer hollow sphere; or
  • the concentration of the template particles is 0. lwt% ⁇ 40wt ° /.
  • the reaction temperature is 0 ° C to 100 ° C, and the reaction time is 0.5 to 24 hours, and the reaction product is deposited on the outer surface of the hollow hollow spherical shell to form a continuous shell layer.
  • the mixture is centrifuged to obtain a composite hollow sphere in which metal and inner layer growth inorganic substances are grown on the outer surface of the polymer hollow spherical shell.
  • the polymer template is removed to obtain a double-layered metal-inorganic hollow sphere, that is, the hollow metal sphere contains an inorganic hollow sphere, and the obtained inorganic hollow sphere can move in the hollow metal sphere; or
  • the initiator concentration is 0. 01wt% ⁇ 20wt%
  • the concentration of the template particles is 0. lwt% ⁇ 40wt%
  • the reaction temperature is 0'C ⁇ 100°C
  • the reaction time was 0.5 to 24 hours, and the reaction product was deposited on the outer surface of the hollow shell of the polymer to form a continuous shell layer.
  • the mixture is centrifuged to obtain a composite hollow sphere in which an organic substance and an inner layer of inorganic substances are grown on the outer surface of the hollow shell of the polymer.
  • the concentration of the inorganic precursor in the reaction solution is 0. 01wt% ⁇ 5 ⁇ 24 ⁇
  • the reaction time is 0. 5 ⁇ 24 hours, the reaction time is 0. 5 ⁇ 24 hours, the reaction time is 0. 5 ⁇ 24 hours, the reaction time is 0. 5 ⁇ 24 hours
  • the reaction product is deposited on the outer surface of the hollow shell of the polymer to form a continuous shell.
  • centrifugal cleaning is performed to obtain a composite hollow sphere in which an inorganic substance and an inner layer growing metal are grown on the outer surface of the polymer hollow spherical shell.
  • the polymer template is removed to obtain a two-layer inorganic-metal hollow sphere, that is, the inorganic hollow sphere contains a hollow metal sphere, and the obtained hollow metal sphere can move in the inorganic sphere; or
  • Rt% ⁇ 30wt%, reducing agent, the metal ion salt concentration in the reaction liquid is controlled to 0. 0 rt% ⁇ 30wt%, reducing agent, the metal hollow salt solution and the reducing agent solution are added to the reaction liquid.
  • the concentration of the template is 0. 01wt% ⁇ 30wt%
  • the concentration of the template particles is 0. lwt% ⁇ 40wt%
  • the reaction temperature is 0 ° C ⁇ 100 ° C
  • the reaction time is 0. 5 ⁇ 24 hours
  • the reaction product is deposited in the polymer hollow sphere
  • the outer surface of the casing forms a continuous shell.
  • centrifugal washing is carried out to obtain a composite hollow sphere in which metal is grown on the outer surface and the inner layer of the hollow shell of the polymer. Removing the polymer template to obtain a two-layer structure metal hollow sphere, that is, the metal hollow sphere contains a metal hollow sphere, and the obtained inner metal hollow sphere can move in the outer metal sphere; or
  • the concentration of the initiator is 0. 01wt% ⁇ 20wt%
  • the concentration of the template particles is 0. lwt% ⁇ 40wt%
  • the reaction temperature is 0 ° C ⁇ 100 ° C
  • the reaction time is 0. 5 ⁇ 24 hours
  • the reaction product is deposited in the polymerization
  • the outer surface of the hollow spherical shell forms a continuous shell.
  • the mixture is centrifuged to obtain a composite hollow sphere in which an organic substance and an inner layer of metal are grown on the outer surface of the hollow shell of the polymer.
  • the concentration of the inorganic precursor in the reaction solution is 0. 01wt% ⁇ 5 ⁇ 24 ⁇ ,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,
  • the concentration of the template particles is 0. lwt% ⁇ 40wt%
  • the reaction temperature is 0°C
  • the concentration of the template is 0. 01wt% ⁇ 30wt%
  • the concentration of the template particles is 0. lwt% ⁇ 40wt%
  • the reaction temperature is 0°C. ⁇ 10 (TC, reaction time 0. 5 ⁇ 24 hours
  • the reaction product is deposited on the outer surface of the hollow shell of the polymer to form a continuous shell.
  • centrifugal cleaning is performed to obtain metal on the outer surface of the hollow shell of the polymer.
  • a composite hollow sphere with an inner layer of organic matter The polymer template is removed to obtain a double-layered metal-organic hollow sphere, that is, the hollow sphere of the metal contains an organic hollow sphere, and the obtained hollow hollow sphere can move in the hollow sphere of the metal;
  • the concentration of the template particles is 0. lwt% ⁇ 40wt%
  • the reaction temperature is 0 ° C ⁇ 100 ° C
  • the reaction time is 0. 5 ⁇ 24 hours
  • the reaction product is deposited on the outer surface of the hollow shell of the polymer to form a continuous shell .
  • the aqueous solution of the reaction solution is immersed in the aqueous solution of the reaction solution.
  • the template particles are kept at a concentration of 0. lwt% ⁇ 40. 0wt%, the aqueous solution of the reaction component is infiltrated into the polymer hollow sphere template.
  • the cavity is centrifuged and the solution that has not penetrated into the cavity of the hollow balloon template is centrifuged. 01 ⁇ % ⁇ 10. (1 ⁇ 21% ⁇ constant)
  • the polymer hollow spheres containing the aqueous solution of the reaction component are added to the alcohol solution of the inorganic precursors, and the inorganic precursor is maintained at 0. 01wt% ⁇ 10.
  • the concentration of the template is maintained at 0. lwt% ⁇ 40.
  • the reaction temperature is 0 ° C ⁇ 100 ° C
  • the reaction time is 0. 5 ⁇ 24 hours
  • the reaction is completed, centrifugal cleaning, the surface is obtained.
  • a hollow sphere of a polymer template with a burr-like substance and an inorganic material, the hydrophilic channel of which is shaped, expanded, or even protruded from the sphere, and the inner layer of the shell generates a continuous material;
  • the concentration of the template particles is maintained at 0. lwt% ⁇ 40. 0wt%, the reaction temperature is 0°C ⁇ 100°C, the reaction time is 0. 5 ⁇ 24 hours, the reaction is completed, and the centrifugal cleaning is performed to obtain the surface burr-like substance.
  • the polymer template is a composite hollow sphere of metal, the hydrophilic channel of which is complexed, expanded, and even extended out of the sphere.
  • the inner layer of the casing generates a continuous material; or
  • the initiator solution is infiltrated into the cavity of the polymer hollow sphere template, and after reaching equilibrium, the solution that has not penetrated into the cavity of the polymer hollow sphere template is centrifuged and washed away. 01% ⁇ 10. 0%% of a constant concentration; in a constant concentration of 0. 01% ⁇ 10. 0%%; The reaction is completed.
  • the reaction temperature is 0. 5 ⁇ 24 hours, the reaction time is 0. 5 ⁇ 24 hours or so, the reaction is completed.
  • the reaction temperature is 0. lwt% ⁇ 40.
  • Centrifugal cleaning that is, a hollow sphere in which a polymer template having a burr-like substance on the surface is combined with an organic substance, the hydrophilic passage is reshaped, expanded, and even protruded from the sphere, and the inner layer of the casing generates a continuous material.
  • a double-layer hollow sphere is obtained, that is, the hollow sphere contains a hollow sphere, but the two hollow spheres are connected by a column, and the inner hollow sphere cannot move in the outer hollow sphere, and the two hollow spheres are concentric.
  • the inner hollow layer obtained by the step (1.1) and the composite hollow sphere of the channel growth inorganic substance are dispersed in the alcohol solution, and the inorganic precursor solution and the aqueous solution of the reaction component are added to control the concentration of the inorganic precursor in the reaction liquid.
  • 01 ⁇ % ⁇ 40wt% The concentration of the template particles is 0. lwt% ⁇ 40wt%, the reaction temperature is 0 °C ⁇ 100 °C, the reaction time is 0. 5 ⁇ 24 hours, the reaction product is deposited on the outer surface of the hollow shell of the polymer to form a continuous shell.
  • the mixture is centrifuged to obtain a composite hollow sphere in which the inorganic body is grown on the outer surface, the inner layer and the channel of the hollow shell of the polymer.
  • the polymer template is removed to obtain a double-layered inorganic hollow sphere, that is, the hollow sphere contains a hollow sphere, and the obtained inorganic hollow sphere has an inorganic column connected between the two hollow spheres, and the inner hollow sphere cannot move in the outer hollow sphere, Hollow ball concentric; or
  • the concentration of the metal ion salt in the reaction solution is 0. 01wt% ⁇ 30wt%, the concentration of the metal ion salt in the reaction solution is 0. 01wt% ⁇ 30wt%, 5 ⁇ 24 ⁇ ,
  • the reaction product is deposited on the polymer.
  • the concentration of the template is 0. 01wt% ⁇ 30wt%, the concentration of the template particles is 0. lwt% ⁇ 40wt%, the reaction temperature is 0'C ⁇ 100 °C, the reaction time is 0. 5 ⁇ 24 hours, the reaction product is deposited on the polymer.
  • the outer surface of the hollow spherical shell forms a continuous shell.
  • the mixture is centrifuged to obtain a composite hollow sphere in which a metal and an inner layer and a channel-grown inorganic substance are grown on the outer surface of the polymer hollow spherical shell.
  • the polymer template is removed to obtain a double-layered metal-inorganic hollow sphere, that is, the hollow metal sphere contains an inorganic hollow sphere, and the obtained double-layer hollow sphere has an inorganic column connected between the two hollow spheres, and the inorganic hollow sphere Can't move in the hollow metal ball, the two hollow balls are concentric; or
  • the concentration of the template particles is 0. lwt% ⁇ 40wt%
  • the reaction temperature is 0°C ⁇ 100 ° C
  • reaction time 0. 5 ⁇ 24 hours
  • the reaction product is deposited on the outer surface of the polymer hollow spherical shell to form a continuous shell.
  • the mixture is centrifuged to obtain a composite hollow sphere in which an organic substance and an inner layer and a channel-grown inorganic substance are grown on the outer surface of the polymer hollow spherical shell.
  • the polymer template is removed to obtain a two-layer organic-inorganic hollow sphere, that is, the organic hollow sphere contains an inorganic hollow sphere, and the obtained double-layer hollow sphere has an inorganic column connected between the two hollow spheres, and the inorganic hollow sphere Cannot move in the hollow sphere of organic matter, the two hollow spheres are concentric; or
  • the weight of the inorganic precursor in the reaction solution is 0. 01wt.
  • the weight of the inorganic precursor in the reaction solution is 0. 01wt % ⁇ 3( rt%, the final concentration of the aqueous solution of the reaction component is 0. lwt% ⁇ 50wt%, the concentration of the template particles is 0. lwt% ⁇ 40wt ° /., the reaction temperature 0 ° C ⁇ 100 ° C, reaction time 0. 5 ⁇ 24 hours, the reaction product is deposited on the outer surface of the hollow shell of the polymer to form a continuous shell. After the reaction is completed, centrifugal cleaning is performed to obtain inorganic and inner layers and channel growth on the outer surface of the hollow shell of the polymer hollow shell. Metal composite hollow sphere.
  • the polymer template is removed to obtain a two-layer structure inorganic-metal hollow sphere, that is, the inorganic hollow sphere contains a metal hollow sphere, and the obtained double-layer hollow sphere has two metal spheres connected by a hollow column. , the hollow metal sphere cannot move in the inorganic sphere, and the two hollow spheres are concentric; or
  • the ionic salt concentration of the metal ionic salt in the reaction liquid is 0.11% by weight to 30% by weight. 5 ⁇ 24 ⁇ ,
  • the reaction product is deposited in the polymerization.
  • the concentration of the template is 0. 01wt% ⁇ 30wt%, the concentration of the template particles is 0. lwt% ⁇ 40wt%, the reaction temperature is 0°C ⁇ 100°C, the reaction time is 0. 5 ⁇ 24 hours, the reaction product is deposited in the polymerization.
  • the outer surface of the hollow spherical shell forms a continuous shell. After the reaction is completed, the mixture is centrifuged to obtain a composite hollow sphere in which metal and inner layer and channel growth metal are grown on the outer surface of the polymer hollow spherical shell.
  • the polymer template is removed to obtain a double-layered metal hollow sphere, that is, the metal hollow sphere contains a metal hollow sphere, and the obtained double-layer hollow sphere has a metal column connected between the two hollow spheres, and the inner metal hollow sphere cannot be in the outer hollow sphere. Movement, two hollow balls concentric; or
  • the polymer template is removed to obtain a two-layer structure organic-metal hollow sphere, that is, the organic hollow sphere contains a metal hollow sphere, and the obtained double-layer hollow sphere has a metal column connected between the two hollow spheres, and the metal hollow sphere cannot be hollow in the organic matter.
  • the concentration of the inorganic precursor in the reaction liquid is 0. 01wt /. 5 ⁇ 24 ⁇
  • the reaction time is 0. 5 ⁇ 24, the reaction time is 0. 5 ⁇ 24 Hours, the reaction product is deposited on the outer surface of the polymer hollow sphere shell to form Continuous shell. After the reaction is completed, the mixture is centrifuged to obtain a composite hollow sphere in which an inorganic substance, an inner layer and a channel-growing organic substance are grown on the outer surface of the hollow sphere of the polymer.
  • the polymer template is removed to obtain a two-layer structure inorganic-organic hollow sphere, that is, the inorganic hollow sphere contains an organic hollow sphere, and the obtained double-layer hollow sphere has an organic column connected between the two hollow spheres, and the organic hollow sphere cannot be Intra-spherical ball movement, two hollow balls concentric; or
  • the double-layered metal-organic hollow sphere that is, the hollow sphere of the metal contains an organic hollow sphere, and the obtained double-layer hollow sphere has an organic column connected between the two hollow spheres, and the organic hollow sphere cannot move in the hollow sphere of the metal, and the hollow Ball concentric; or
  • the mixture is centrifuged to obtain a composite hollow sphere in which organic matter is grown on the outer surface of the hollow shell of the polymer and the inner layer and the channel.
  • the polymer template is removed to obtain a double-layered organic hollow sphere, that is, the organic hollow sphere contains an organic hollow sphere, and the obtained double-layer hollow sphere has an organic column connected between the two hollow spheres, and the inner hollow sphere cannot move in the outer hollow sphere. , the two hollow balls are concentric.
  • the outer surface of the hollow sphere of the polymer also becomes a hydrophilic surface, that is, the intermediate layer is oleophilic, and the inner layer and the outer surface are three-layer shell which is ice-friendly, and the surface modification polymerization is performed.
  • the hollow sphere replaces the polymer hollow sphere template to carry out the reaction, and the composite hollow sphere of a multi-layer structure can be produced in one step. By removing the template polymer with a selective solvent, a two-layer hollow sphere can be obtained.
  • the inorganic polymer precursors are immersed in a concentration of 0. 01wt% ⁇ 60. 0wt% of the inorganic precursor solution, the template particles in the solution to maintain a concentration of 0. lwt% ⁇ 40. 0wt%, make inorganic substances
  • the precursor solution penetrates into the cavity and hydrophilic layer of the modified polymer hollow sphere template, and after reaching equilibrium, the solution that has not penetrated into the cavity is centrifuged and washed away.
  • the obtained modified polymer hollow sphere containing the inorganic precursor solution is then added to the aqueous solution of the reaction component with stirring. ⁇ 40.
  • the double-layered inorganic hollow sphere can be obtained by removing the template polymer with a selective solvent; or 01wt% ⁇ 60.
  • the weight of the modified polymer hollow spheres containing the aqueous solution of the reaction mixture was added to a concentration of 0. 01wt% ⁇ 60. Owt% in the inorganic precursor solution.
  • the temperature of the modified polymer hollow sphere is controlled to be 0. lw « ⁇ 40. 0wt%, the reaction temperature is 0 ° C ⁇ 100.
  • the reaction time is about 0.5 to 24 hours, the reaction is completed, and the mixture is centrifuged to obtain a multilayer composite hollow sphere of a polymer and an inorganic material.
  • a two-layer inorganic hollow sphere can be obtained.
  • reaction temperature 0°C ⁇ 100°C
  • reaction time 0. 01wt% ⁇ 60. 0%% of the reducing agent solution.
  • the reaction is completed and centrifuged to obtain a multi-layer composite hollow sphere of polymer and metal.
  • the double-structured metal hollow sphere can be obtained by removing the template polymer with a selective solvent;
  • 0. 01wt% ⁇ 60. 0wt% of the reducing agent solution is infiltrated into the hollow cavity of the modified polymer hollow sphere particles and the hydrophilic layer, and then the obtained modified polymer hollow sphere containing the reducing agent solution is added under stirring.
  • a concentration of 0. 01wt% ⁇ 60. 0wt% of the metal ion salt solution is maintained at 0. lwt% ⁇ 40. 0wt%
  • the reaction temperature is 0 ° C ⁇ 10 (TC, reaction time 0. 5 ⁇ 24 hours or so, the reaction is completed, centrifugal cleaning, the same polymer Multi-layer composite hollow sphere with metal.
  • the double-structured metal hollow sphere can be obtained by removing the template polymer with a selective solvent.
  • the polymer monomer solution is infiltrated into the cavity and hydrophilic layer of the modified polymer hollow sphere, and after reaching equilibrium, the solution not infiltrated into the hollow cavity of the modified polymer hollow is centrifuged and washed.
  • the modified polymer hollow spheres of the monomer solution are added to 0. 01wt% ⁇ 30. 0wt% in the initiator solution.
  • the inert gas is introduced into the reaction vessel to control the concentration of the template particles in the reaction solution to be kept at 0. Lwt% ⁇ 40.
  • reaction temperature 0 °C ⁇ 100 ° C
  • reaction time 0. 5 ⁇ 24 hours or so
  • the reaction is completed, centrifugal cleaning, that is, a multi-layer composite hollow sphere of polymer and organic matter is obtained.
  • the solvent removes the template polymer to produce a two-layer organic hollow sphere.
  • the initiator solution is infiltrated into the cavity of the modified polymer hollow sphere and the hydrophilic layer, and then the modified polymer hollow sphere containing the initiator solution is added to a concentration of 0. 01 ⁇ /. ⁇ 4 (1 ⁇ 2 «)
  • the polymer monomer solution The inert gas is introduced into the reaction vessel, and the concentration of the template particles in the reaction solution is kept at 0. lwt ° / . ⁇ 40 wt%, the reaction temperature is 0 ° C ⁇ 100 ° C, The reaction time is about 0.5 to 24 hours, the reaction is completed, and the mixture is centrifuged to obtain a multilayer composite hollow sphere of polymer and organic matter.
  • the template polymer can be removed by a selective solvent to obtain a two-layer organic hollow sphere.
  • Preparation method of polymer composite hollow sphere by swelling polymerization method Steps: Dispersing the polymer hollow sphere template particles in water, adding a monomer and a crosslinking agent, or a monomer and a crosslinking agent and an organic solvent, swelling the polymer hollow sphere template shell by a monomer or an organic solvent, and Lwt% ⁇ 20wt% ⁇
  • the body and the initiator is introduced into the polymer hollow spherical shell layer, and then the polycondensation, polycondensation or ring-opening polymerization, the inert gas is introduced into the reaction vessel, the concentration of the template particles in the reaction solution is 0.
  • the reaction The monomer concentration is 0. lwt% ⁇ 20wt%, the initiator concentration is 0.01wt% ⁇ 10wt%, the organic solvent concentration is 0wt% ⁇ 20wt%, the swelling time is 0.5 ⁇ 24 hours, and the reaction temperature is 20 °C ⁇ 250° C, reaction time 0.5 to 48 hours.
  • a composite hollow sphere of a polymer hollow sphere and an organic substance can be obtained.
  • the outer diameter of the polymer hollow sphere template particles is 0.02Mm ⁇ 10to, and the cavity volume is 10 ⁇ 95% of the whole microsphere.
  • the synthetic methods used are spray drying method, block copolymer self-assembly method, acid Alkali swelling method, dynamic swelling method, multiphase emulsion polymerization method.
  • the inner hydrophilic polymer of the polymer hollow sphere template comprises polystyrenesulfonic acid, polymethacrylic acid, polyacrylic acid, polyvinyl alcohol, polyamide, polyvinylpyrrole, poly(2-vinylpyrrolidone). Precipitate), poly(4-vinylpyridine), polyhydroxyethyl methacrylate, polyvinyl ester, polyoxyethylene or polyvinyl ammonium chloride.
  • the outer lipophilic polymer of the polymeric hollow sphere template comprises polystyrene, polymethyl methacrylate, polyethyl methacrylate, polybutyl methacrylate, polybutyl methacrylate, polymethyl Acrylic acid cinnamic acid ethyl ester, polymethyl acrylate, polyethyl acrylate, polybutyl acrylate, polybutyl acrylate, polyoxypropylene, polydimethylsilyl, polyvinyl butyrate or polyisobutylene.
  • the selective solvent for removing the polymer template is chloroform, toluene, tetrahydrofuran or N,N-dimethylformamide or the like.
  • the hydrophilic modification of the polymer hollow sphere is carried out by hydrophilic modification of a commercially available or self-made polymer hollow sphere (having a diameter of 0.02 m to 10 Mm and a cavity size of 10 to 95% of the entire microsphere size).
  • the modification methods include electrostatic adsorption, sulfonation treatment, hydrolysis reaction, surface grafting and the like.
  • the inorganic precursor solution is Si (0CH 3 ) 4 , Si (0CH 2 C3 ⁇ 4), Si ⁇ 0CH(C3 ⁇ 4) 2 ⁇ 4 , Si(0CH 2 C CH 2 CH 3 ) 4 , an alcohol solution of Na 2 SiO 3 ;
  • the aqueous solution of the reaction component is an alcoholic solution of water (0. lwt ° / ⁇ 100 wt%), and its P H is adjusted with 35 % concentrated hydrochloric acid or 25 w « concentrated ammonia water The value is 1 ⁇ 13.
  • the inorganic precursor solution is TiCl 4 , Ti(0CH 3 ) 4 , Ti(0C C ) 4 , Ti ⁇ 0CH(CH 3 ) 2 ⁇ 4 , Ti (0CH 2 CH 2 CH 2 C ) 4 , T alcohol 0 4 alcohol solution;
  • the reaction component aqueous solution is water alcohol solution (0. lwt% ⁇ 100 wt%), with 35 % concentrated hydrochloric acid or 25 wt% concentrated ammonia water to adjust its pH It is 1 to 13.
  • the inorganic precursor solution is SnCl 4 , Sn(0C3 ⁇ 4) 4 , Sn(0CH 2 CH 3 ) 4 , Sn ⁇ 0CH(CH 3 ) 2 ⁇ Sn
  • an aqueous solution of the reaction component is an alcoholic solution of water (0.1 wt% to 100 wt%), using 35 % concentrated hydrochloric acid or 25 wt ° /. Concentrated ammonia water adjusts its pH to 1 ⁇ 13.
  • the inorganic precursor solution is ZrCl 4 , Zr(0CH 3 ) 4 , Zr (0C CH 3 ) 4 , Zr ⁇ 0CH(C3 ⁇ 4) 2 ⁇ 4 , Zr (0C C CH 2 C3 ⁇ 4) 4 , Zr (S0 4 ) 2 alcohol solution;
  • the reaction component aqueous solution is water alcohol solution (0. Lwt% ⁇ 10 (kt%), the pH is adjusted to 1 ⁇ 13 with 35wt% concentrated hydrochloric acid or 25wt%/concentrated ammonia water.
  • the inorganic precursor solution is A1C1 3 , A1 (0CH 3 ) 3 , A1 (0CH 2 CH 3 ) 3 , A1 ⁇ 0CH(C ) 2 ⁇ 3 , Al (0CH 2 CH 2 C CH 3 ) 3 , Al 2 (S0 4 ) 3 alcohol solution;
  • the reaction component aqueous solution is water alcohol solution (0. lwt% ⁇ 100wt%), with 35wt% hydrochloric acid or 25wt
  • the concentrated ammonia water is adjusted to have a pH of 1 to 13.
  • the inorganic precursor solution is V0 (0CH 3 ) 3 , V0(0CH 2 C ) 3 , VO ⁇ 0CH(CH 3 ) 2 ⁇ 3 , V0 (0CH 2 C C3 ⁇ 4C3 ⁇ 4) 3 alcohol solution;
  • the aqueous solution of the reaction component is an alcoholic solution of water (0. lwt ° / ⁇ ⁇ 100 wt%), with 35 ⁇ « concentrated hydrochloric acid or 25wt ° /. Concentrated ammonia water adjusts its pH to 1 ⁇ 13.
  • the inorganic precursor solution is an alcohol solution of Zn(N0 3 ) 2 , Zn (00CCH 3 ) 2 , ZnCl 2 , Zn (CI ) 2 ; It is a water or alcohol solution of alkali (0. 01wt ° / a ⁇ 30wtt), such as sodium hydroxide, potassium hydroxide or ammonia.
  • the inorganic precursor solution is an aqueous solution of (NH 4 ) 6 H 2 W 12 0 41 , NaW0 3 ; ⁇ 100wt%), the pH is adjusted to 1 ⁇ 13 with 35% concentrated hydrochloric acid or 25% concentrated ammonia water.
  • the inorganic precursor solution is an aqueous solution of Mo 0 3 2 0;
  • the aqueous solution of the reaction component is an aqueous alcohol solution (0. lwt% to 100 wt%), with a concentration of 35 % Hydrochloric acid or 25 wt% concentrated aqueous ammonia is adjusted to have a pH of 1 to 13.
  • the inorganic precursor solution is an aqueous solution of soluble aluminum, magnesium chloride or sulfate; the aqueous solution of the reaction component is alkali Aqueous solution (0.11% by weight to 30% by weight) such as sodium hydroxide, potassium hydroxide or ammonia.
  • the inorganic precursor solution is Ca(0H) 2 , CaCl 2 , Ba(0H) 2 , or BaCl 2 ⁇ ;
  • the aqueous solution of the reaction component is a solution of C0 3 2 —, P0—, SO—Na+, or K + salt or H 2 C0 3 , H 3 P0 4 , 3 ⁇ 450 4 (0. 01wt°/. ⁇ 30wt%).
  • the inorganic precursor solution is an aqueous solution of a soluble salt of a corresponding metal cation, such as a chloride, a nitrate, or a sulfate; the aqueous solution of the reaction component is sodium sulfide, sulfur An aqueous solution of urea (0. 01wt ° / ⁇ ⁇ 30wt%).
  • the inorganic precursor solution is an aqueous solution of a soluble salt of a metal cation such as chloride, nitrate or sulfate; and the aqueous solution of the reaction component is selenized.
  • An aqueous solution of sodium or sodium hydride (0.11% by weight to 30% by weight). .
  • the inorganic precursor solution is Fe 2
  • An aqueous solution of an alkali 0.11% by weight to 30% by weight, such as sodium hydroxide, potassium hydroxide or aqueous ammonia, or a hydrazine hydrate solution (hrt% ⁇ 6 (kt%)).
  • the metal ion salt solution is an aqueous solution of a corresponding metal ion soluble salt, such as perchlorate. , chloride, nitrate, sulfate;
  • the reducing agent solution is an aqueous solution of a reducing agent, such as an aqueous solution of NaB, LiB (C 2 H 5 ) 3 H, N 2 .
  • the polymer monomer solution is a water or alcohol solution of the corresponding monomer;
  • the solution is an aqueous solution of potassium persulfate, ammonium persulfate or ferric chloride.
  • the polymer monomer solution is a monomeric N-isopropylacrylamide, Acrylic acid, methyl decenoic acid or its water or alcohol solution;
  • the initiator solution is an aqueous solution of potassium persulfate or ammonium persulfate.
  • the composite includes inorganic, metal, organic composites such as Ti0 2 and SiO 2 , Ti0 ⁇ n SnO 2 , TiO 2 and ZnO, gold and silver, palladium and nickel, and the like. Also included are inorganic, metal and organic complexes such as titanium dioxide and triiron tetroxide, polyaniline and ferric oxide, polyacrylic acid and silver.
  • the inert gas is nitrogen or argon or the like.
  • the alcohol solution is methanol, ethanol, propanol, isopropanol, butanol or the like.
  • the shell swelling polymerization method can be used to prepare high performance polymer hollow spheres or composite hollow spheres, such as crosslinked polystyrene, polyacrylate, polyurethane, phenolic resin, unsaturated polyester, epoxy resin, polyacyl. Imine, polyether ketone or polyether sulfone hollow sphere or composite hollow sphere.
  • the cross-linking agent for preparing cross-linked polystyrene, polyacrylate hollow sphere or composite hollow sphere is azobisisobutyronitrile, azobisisoheptanenitrile, dibenzoyl peroxide, peroxydicarbonate Isopropyl ester, potassium persulfate or ammonium persulfate; the monomer is styrene, divinylbenzene, methyl acrylate, ethyl acrylate, propyl acrylate or butyl acrylate;
  • the crosslinking agent for preparing the polyurethane hollow sphere or the composite hollow sphere is polyether diol, polyester diol or 1, 4-butanediol; the monomer is hexamethylene diisocyanate or toluene diisocyanate;
  • the crosslinking agent for preparing the phenolic resin hollow sphere or the composite hollow sphere is phenol, o-cresol, p-cresol, resorcin or bisphenol A; the monomer is formaldehyde, trioxane, acetaldehyde, trimer Acetaldehyde or furfural;
  • the crosslinking agent for preparing the unsaturated polyester hollow sphere or the composite hollow sphere is ethylene glycol, propylene glycol, 1, 3-butanediol, polyether diol or polyester diol; the monomer is bismuth maleate ;
  • the crosslinking agent for preparing the epoxy resin hollow sphere or the composite hollow sphere is hexamethylene diisodecanoate, toluene diisocyanate, phthalic anhydride, phthalic anhydride, maleic anhydride, ethylenediamine, and hexan An amine or trimethyltetramine; the monomer is bisphenol A epoxy or phenolic epoxy;
  • the crosslinking agent for preparing the polyimide hollow sphere or the composite hollow sphere is p-phenylenediamine or hexamethylenediamine; the monomer is bismaleic anhydride or pyromellitic anhydride;
  • the crosslinking agent for preparing the polyether ketone or the polyether sulfone hollow sphere or the composite hollow sphere is 4,4-difluorobenzophenone or 4,4-dichlorodiphenyl sulfone; the monomer is hydroquinone Or tetramethylbiphenyldiol.
  • the organic solvent used to swell the polymer hollow spherical shell is chloroform, benzene, toluene, xylene, tetrahydrofuran, hydrazine, hydrazine-dimethylformamide, hydrazine, hydrazine-dimethylacetamide, dimethyl Sulfone, acetone, cyclohexane.
  • the composite hollow spheres and hollow spheres prepared by the invention have wide applications -
  • a high-performance catalyst can be prepared to form a hollow sphere of a catalyst material.
  • the catalyst hollow sphere is composed of nanoparticles, and the large specific surface area also ensures the liquidity of the liquid gas.
  • Semiconductors such as zinc oxide and cadmium sulfide can be used as solar cell materials by utilizing their ultraviolet light absorption and photoelectric conversion properties, and can also be used as photocatalytic materials, which are widely used in antibacterial deodorization, sewage treatment, and purification of exhaust gas. , Photolysis water, etc., can also be used as gas sensors, dielectric ceramics.
  • an electrode active material an electrochemical catalytic active material, a metal anticorrosive material, a chemical or electrochemically adjustable gas separation membrane, an electrochromic element, a living body can be prepared. Sensors, etc.
  • Functional materials can also be used as insulating materials, thermal insulation materials, sound absorbing materials, conductive materials, ordered magnetic materials, photoelectric functional materials, and the like.
  • the preparation method and product features of the invention are as follows:
  • the preparation method of the invention has wide adaptability, and can prepare a series of hollow spheres and composite hollow spheres of different materials and forms;
  • the hollow sphere and the composite hollow sphere of the present invention not only have good dispersibility, but also have good strength and dimensional stability;
  • the size of the prepared hollow sphere and composite hollow sphere can be adjusted within the range of 10 1 to 10 4 ;
  • the shape of the hollow sphere and the composite hollow sphere is adjustable, and the composition and thickness of the casing are controllable;
  • Figure 1 Schematic diagram of a polymer hollow sphere template applied in an embodiment of the present invention.
  • FIG. 1 Transmission electron micrograph of a polystyrene-polypropylene/titanium oxide composite hollow sphere of Example 1 of the present invention.
  • Fig. 3 Transmission electron micrograph of a titanium dioxide hollow sphere of Example 1 of the present invention.
  • Fig. 4 Scanning electron micrograph of a titanium oxide tetragonal iron oxide composite hollow sphere of Example 8 of the present invention.
  • Figure 5 is a scanning electron micrograph of a burr type titanium dioxide/polystyrene-polyacrylic composite hollow sphere of Example 10 of the present invention.
  • the polystyrene-polyacrylic hollow sphere template has a polystyrene outer layer of polystyrene and an inner layer of polyacrylic acid having an outer diameter of 500 rai and a shell thickness of 100 nm. 0. lg template particles were dispersed in lg tetrabutyl titanate, saturated adsorption for 4 hours, the hollow spheres adsorbed tetrabutyl titanate were sedimented by a high-speed centrifuge, and 10 g of water in ethanol (40 wt%) was added.
  • the hydrolysis reaction was carried out for 4 hours to obtain a composite hollow sphere in which titanium dioxide was grown in the inner layer of the shell using polystyrene-polyacrylic acid hollow spheres as a template.
  • the hollow sphere of this composite structure was removed from polystyrene and polyacrylic acid with chloroform to obtain hollow spheres of titanium dioxide.
  • the results of transmission electron microscopy showed that the hollow titania sphere consisted of 30 50 nm particles with a shell thickness of 60 nm and the size of the cavity. 250nm
  • the prepared composite hollow spheres are sintered at 45 CTC for 2 hours to obtain hollow spheres of crystalline titania, and the XRD results indicate that the crystal form is anatase; the composite hollow spheres are sintered at 600 ° C for 2 hours to obtain crystalline titanium dioxide. Hollow spheres, XRD results show that the crystal form is anatase and rutile composite.
  • Example 2 Preparation of polystyrene-polymethacrylic acid/magnetic ferroferric oxide composite hollow spheres and ferroferric oxide hollow spheres O.
  • polystyrene-polymethacrylic acid hollow structure emulsion particles the outer diameter of which is lOOOran, the thickness of the shell layer is 150nm, dispersed in lg of 25 « ferric chloride and 19%% ferrous chloride mixed solution, saturated adsorption for 4 hours, the polymer hollow spheres with adsorbed solution are centrifuged by high-speed centrifuge , redispersed in 10g of 15wt ° /. Ammonia water was hydrolyzed for 4 hours to obtain a composite hollow sphere in which polystyrene-polymethacrylic acid hollow spheres were used as a template and ferroferric oxide was grown in the inner layer of the shell.
  • the hollow sphere of this composite structure was subjected to removal of polystyrene and polymethacrylic acid with chloroform to obtain a hollow sphere of triiron tetroxide.
  • the results of transmission electron microscopy showed that the hollow triiron tetroxide consisted of 50-100 nm particles with a shell thickness of 200 nm and a cavity size of 400.
  • Example 3 Polymethyl methacrylate-polyacrylic acid/calcium carbonate composite hollow sphere And preparation of calcium carbonate hollow spheres O.
  • polymethyl methacrylate-polyacrylic acid hollow structure emulsion particles the outer diameter of which is 100nm, the thickness of the shell layer is 20nm, dispersed in 15wt% calcium chloride solution, saturated adsorption for 4 hours, will be adsorbed
  • the hollow spheres of the calcium chloride solution were centrifuged by a high-speed centrifuge, dispersed in 10 g of a 15 wt% aqueous solution of sodium carbonate, and the pH was adjusted to 9 with 25 wt% of ammonia water for 4 hours to obtain polymethyl methacrylate-poly.
  • the acrylic hollow sphere is a composite hollow sphere in which the template calcium carbonate is grown in the inner layer of the shell.
  • the composite hollow spheres were subjected to removal of polymethyl methacrylate and polyacrylic acid with chloroform to obtain hollow spheres of calcium carbonate.
  • the results of transmission electron microscopy showed that the hollow calcium carbonate sphere consisted of 20 nm particles with a shell thickness of 20 nm and a cavity size of 20 nra.
  • 'Example 4 Preparation of polystyrene-polyacrylic acid/cadmium sulfide composite hollow spheres and cadmium sulfide hollow spheres
  • polystyrene-polyacrylic acid hollow structure emulsion particles the outer diameter of 300nm, the thickness of the shell layer is 60nm, dispersed into 2 (kt% cadmium nitrate aqueous solution, saturated adsorption for 24 hours, will adsorb the solution
  • the hollow spheres were centrifugally sedimented by a high-speed centrifuge, dispersed in 10 g of a 20 wt% aqueous solution of sodium sulfide, and reacted for 4 hours to obtain a composite hollow sphere in which cadmium sulfide was grown in the inner layer of the shell by using polystyrene-polyacrylic acid hollow spheres as a template.
  • polystyrene-poly 2 vinyl pyridine hollow structure emulsion particles 0. lg polystyrene-poly 2 vinyl pyridine hollow structure emulsion particles, the outer diameter of 100 dishes, the thickness of the shell layer is 20nm, dispersed in 15wt% silver nitrate solution, saturated adsorption for 4 hours, will adsorb
  • the polymer hollow spheres of the silver nitrate solution were sedimented by a high-speed centrifuge, dispersed in 10 g of 20 t% hydrazine hydrate, and hydrolyzed for 4 hours to obtain a polystyrene-poly-2-vinylpyridine hollow sphere as a template.
  • the polystyrene-polyacrylic acid/titanium dioxide composite hollow sphere was prepared according to Example 1, and the composite particles were dispersed in lg of 25% iron chloride and 19% ferrous chloride mixed solution, and saturated for 4 hours.
  • the polymer hollow spheres to which the solution was adsorbed were sedimented by a high-speed centrifuge, dispersed in 10 g of 15 wt% aqueous ammonia, and hydrolyzed for 4 hours to obtain a polystyrene-polyacrylic acid/titanium dioxide magnetic tetraoxide composite hollow sphere.
  • the hollow sphere of this composite structure was subjected to removal of polystyrene and polyacrylic acid with chloroform to obtain a composite hollow sphere of titanium oxide and triiron tetroxide.
  • Lg The polystyrene-polyacrylic acid/titanium dioxide composite hollow spheres, the composite particles 0. lg
  • the aniline was added to the mixture.
  • the ocyanamine was added to the mixture.
  • the ocyanamine was added to the mixture.
  • the reaction was carried out for 24 hours in an ice water bath to obtain a polystyrene-polyacrylic acid/titanium oxide polyaniline composite hollow sphere.
  • Example 10 Preparation of burr type titanium dioxide/polystyrene-polymethacrylic acid composite hollow sphere and edgy type titanium dioxide hollow sphere
  • the hollow spheres of the composite structure were removed with polystyrene and polymethacrylic acid by chloroform to obtain burred titanium dioxide hollow spheres.
  • the results of transmission electron microscopy showed that the hollow titanium dioxide spheres were composed of 50-100 nm particles with a shell thickness of 100 nm.
  • the size of the cavity is 600 nm.
  • the titanium dioxide burr is 50 to 200 nm long, 20 to 100 nm wide, and 10 to 150 nm high.
  • Example 11 Preparation of burr-type silver/polystyrene-poly 4-vinylpyridine composite hollow spheres and burr-type silver hollow spheres An emulsion containing O.
  • polystyrene-poly-4-vinylpyridine polymer hollow spheres having an outer diameter of 300 nm, a shell layer thickness of 60 nm, dispersed in 10 g of a 20 wt% hydrazine hydrate solution, and immersed for 24 hours.
  • the hollow polymer spheres adsorbed with the hydrazine hydrate solution were centrifuged and sedimented by a high-speed centrifuge, and then dispersed in 20 g of a lwt% silver nitrate solution for 4 hours to obtain a hollow sphere of polystyrene-poly-4-vinylpyridine polymer.
  • Example 12 Preparation of a blister-type polyaniline/polystyrene-polyacrylic composite hollow sphere and a burr-type polyaniline hollow sphere
  • the thickness of the shell layer is 80 nm, dispersed in 5 g of 20% aqueous solution of ferric chloride, and saturated for 24 hours.
  • the polymer composite hollow spheres to which the solution has been adsorbed are centrifugally sedimented by a high-speed centrifuge, dispersed in 10 g of water, and stirred. 0.
  • the polystyrene-polyacrylic acid polymer hollow sphere was used as a template, and polyaniline was grown in the inner layer and channel of the shell. And protruding from the surface to form a donkey.
  • the hollow sphere of this composite structure was subjected to removal of polystyrene and polyacrylic acid with chloroform to obtain a burred polyaniline hollow sphere.
  • Example 13 The outer surface of the shell was grown to form a silica/polystyrene-polyacrylic composite hollow sphere and a silica hollow sphere.
  • Example 14 The shell surface was grown on the outer surface of the shell to prepare a gold/polystyrene-polyoxyethylene composite hollow sphere and a gold hollow sphere.
  • the lg polystyrene-polyoxyethylene polymer hollow spheres having an outer diameter of 40 nra, a thickness of the shell layer of lOnm, dispersed in 10 g of water, adding lg of 5% hydrazine hydrate and 0.5 g of chloroauric acid, reacting for 2 hours
  • a composite hollow sphere in which gold is grown on the outer surface of the shell is obtained by using a polystyrene-polyoxyethylene hollow sphere as a template.
  • the composite hollow sphere was removed from polystyrene and polyoxyethylene by chloroform to obtain a gold hollow sphere.
  • the hollow gold sphere consisted of 5 ⁇ 10 nm particles with a shell thickness of 20 nm and the size of the cavity was 40nm.
  • Example 15 Growth of shell layer on outer surface of shell, preparation of polyaniline/polystyrene-polymethacrylic acid composite hollow sphere and polyaniline hollow sphere
  • polystyrene-polymethacrylic acid hollow structure emulsion particles having an outer diameter of 400 nm, a shell layer having a thickness of 80 nm, and dispersed in 10 g of water.
  • Put nitrogen in the reaction vessel add 2g of 22.8% aqueous ammonium persulfate solution, stir After mixing for 30 minutes, another 0.5 g of aniline was added and reacted in an ice water bath for 24 hours to obtain a composite hollow sphere in which polyaniline was grown on the outer surface of the shell by using polystyrene jf_polymethacrylic acid hollow sphere as a template.
  • the hollow sphere of this composite structure was subjected to removal of polystyrene and polymethacrylic acid with tetrahydrofuran to obtain a polyaniline hollow sphere having a cavity size of 400 nm.
  • Example 16 Preparation of Silica/Titanium Dioxide Multilayer Composite Hollow Sphere and Its Double-Stranded Hollow Sphere
  • the polystyrene-polyacrylic acid/ceria composite hollow sphere was prepared according to Example 1, and the composite particles were dispersed in 10 g of ethanol, and lg ethyl silicate and lg25% aqueous ammonia were added thereto, and the reaction temperature was 40 ° C.
  • a silica/polystyrene-polyacrylic acid/titanium dioxide composite hollow sphere was prepared, which was grown in the inner layer of the polymer hollow sphere shell, and silica was grown on the outer surface of the shell.
  • polystyrene-polymethacrylic acid hollow structure emulsion particles the outer diameter of which is lOOnm, the thickness of the shell layer is 20nm, dispersed to lg of 5 (kt% tetraethyl silicate in ethanol solution, saturated adsorption After 24 hours, the polymer hollow spheres with adsorbed solution were sedimented by high-speed centrifuge, dispersed in 10 g of 15 wt% ammonia water, and hydrolyzed for 4 hours to obtain polystyrene-polymethacrylic acid hollow spheres as a template for dioxide oxidation.
  • the composite particles are redispersed into 10 g of an aqueous solution, and 6 ⁇ 30% of the chloroauric acid solution and 4 g of 5 (hrt% hydrazine hydrate solution are added, the reaction temperature is 40 Torr, and the reaction time is 4 h. That is, a gold/polystyrene-polyacrylic acid/silica composite hollow sphere is prepared, and the silica is grown in the inner layer of the polymer hollow sphere shell, and gold is grown on the outer surface of the shell. Polystyrene and polymethyl are removed by using tetrahydrofuran.
  • polymethyl methacrylate-polyacrylic acid hollow structure emulsion particles the outer diameter of 300nm, the thickness of the shell layer is 60nm, dispersed in lg 20wt% silver nitrate aqueous solution, saturated adsorption for 24 hours, will adsorb
  • the polymer hollow spheres of the solution were sedimented by a high-speed centrifuge, dispersed in 10 g of a 15 wt% hydrazine hydrate solution, and reacted for 4 hours to obtain a polymethyl methacrylate-polyacrylic acid hollow sphere as a template, and silver was grown in the shell.
  • a composite hollow sphere of the inner layer The polymer hollow spheres of the solution were sedimented by a high-speed centrifuge, dispersed in 10 g of a 15 wt% hydrazine hydrate solution, and reacted for 4 hours to obtain a polymethyl methacrylate-polyacrylic acid hollow sphere as a template, and
  • the composite particles were redispersed into 10 g of an aqueous solution, and nitrogen gas was introduced thereto, and 0.5 g of aniline and 3 g of a 30 wt% aqueous solution of ammonium persulfate were added, and the mixture was placed in an ice water bath for 24 hours to obtain polyaniline/polymethyl methacrylate.
  • a polyaniline/silver double-layer hollow sphere is obtained, that is, a hollow sphere containing one silver in the polyaniline hollow sphere.
  • Example 19 Preparation of Silica/Titanium Dioxide Multilayer Composite Hollow Sphere and Concentric Double Layer Hollow Sphere 0. Ig polystyrene-if polymethacrylic acid hollow structure emulsion particles, the outer diameter of which is 400 letters, the thickness of the shell layer is 80nm, centrifuged with ethanol to remove the outer surface water, and then dispersed in 10g of ethanol, 4 times added 0.
  • a hollow sphere of silica titania double-layer structure is obtained, that is, a hollow sphere containing a titanium dioxide in a silica hollow sphere, and a hollow titanium dioxide column is connected between the two hollow spheres, and the hollow is hollow.
  • the ball cannot move in the outer hollow sphere, and the two hollow spheres are concentric.
  • polystyrene-polymethacrylic acid hollow structure emulsion particles having an outer diameter of 200 ⁇ , a shell layer having a thickness of 50 nm, and dispersed at 1 g 20 wt ° /.
  • the sodium borohydride aqueous solution was immersed for 24 hours, and the outer surface solution was removed by centrifugation, and then dispersed in 10 g of water, and 4 mL of 20 wt/ was added in 4 portions.
  • Chloroplatinic acid one hour at a time, the reaction is continued for 8 hours, and the reaction temperature is 20 ° C.
  • the polystyrene-polymethacrylic acid hollow sphere is used as a template to obtain a composite burr of platinum grown in the inner layer and the channel of the shell. Hollow ball. Dispersing the composite particles into 10 g of ethanol, adding 2 g of tetrabutyl titanate and lg water, the reaction temperature is 40 Torr, and the reaction time is 4 h, thereby preparing a titanium dioxide/polystyrene-polymethacrylic acid/platinum composite hollow sphere, the platinum It grows in the inner layer and channel of the polymer hollow sphere shell, while titanium dioxide grows on the outer surface of the shell.
  • a hollow sphere of ruthenium dioxide platinum double-layer structure is obtained, that is, a hollow sphere containing platinum in a hollow sphere of titanium dioxide, and a platinum metal column is connected between the two hollow spheres, and the inner hollow sphere is connected. Can not move in the outer hollow ball, the two hollow balls are concentric.
  • the burr-like polyaniline/polystyrene-polyacrylic composite hollow sphere was prepared according to Example 12, and the composite particles were dispersed in 10 g of ethanol, and lg tetrabutyl titanate and lg water were added thereto, and the reaction temperature was 60 ° C.
  • the reaction time was 4 h, that is, a titanium dioxide/polystyrene-polyacrylic acid/polyaniline composite hollow sphere was prepared, and the polyaniline was grown in the inner layer and the channel of the polymer hollow sphere shell, and the titanium dioxide was grown on the outer surface of the shell.
  • a hollow sphere of titanium dioxide polyaniline double-layer structure is obtained, that is, a hollow sphere containing a polyaniline in a hollow sphere of titanium dioxide, and a polyaniline column is connected between the two hollow spheres, and the inner hollow sphere cannot be outside.
  • the hollow ball moves, and the two hollow balls are concentric.
  • the modified polymer hollow sphere was immersed in 1 g of 50% tetrabutylammonate titanate solution, soaked for 24 hours, centrifuged, and then added to 10 g of 40% water in butanol solution, 40 ° C After reacting for 6 hours, a titanium dioxide/polystyrene-polyacrylic multilayer composite hollow sphere was obtained, and titanium dioxide was grown on the inner layer, the channel and the outer layer of the polymer hollow spherical shell.
  • the hollow sphere of this composite structure was sintered at 45 CTC for 2 hours to remove polystyrene and polyacrylic acid, thereby obtaining a hollow sphere of titanium dioxide double-layer structure.
  • Example 23 Preparation of Silver Multilayer Composite Hollow Sphere and Concentric Double Layer Hollow Sphere
  • the polymer hollow sphere has a three-layer structure in which the outer layer is sulfonated polystyrene, the intermediate layer is polystyrene, and the inner layer is polymethacrylic acid, so that the inner layer and the outer layer of the shell are hydrophilic, and there is Hydrophilic channel.
  • the modified polymer hollow sphere was immersed in 1 g of 20% silver nitrate aqueous solution, soaked for 24 hours, centrifuged, and then added to 10 g of 30% hydrazine hydrate solution, and reacted at 20 ° C for 6 hours to obtain silver/poly.
  • a styrene-polymethacrylic multilayer composite hollow sphere, silver is grown in the inner layer, the channel and the outer layer of the polymeric hollow sphere shell.
  • the hollow sphere of this composite structure was subjected to removal of polystyrene and polymethacrylic acid with N, N-dimethylformamide to obtain a silver double-layer hollow sphere.
  • Example 24 Preparation of polyaniline multilayer composite hollow spheres and concentric double-layer hollow spheres
  • the ball has a three-layer structure in which the outer layer is sulfonated polystyrene, the intermediate layer is polystyrene, and the inner layer is polyacrylic acid. Therefore, the inner layer and the outer layer of the shell are hydrophilic, and there is a hydrophilic passage in the middle.
  • the modified polymer hollow sphere was immersed in 1 g of 30% ferric chloride solution, soaked for 24 hours, centrifuged, and then added to 10 g of water, added with 0.5 g of aniline, and the pH of the reaction solution was adjusted with concentrated hydrochloric acid. The value was 1-2, and the reaction was carried out in an ice water bath for 24 hours to obtain a polyaniline/polystyrene-polyacrylic multilayer composite hollow sphere, and the polyaniline was grown in the inner layer, the channel and the outer layer of the polymer hollow sphere shell.
  • the hollow sphere of this composite structure was subjected to removal of polystyrene and polyacrylic acid with N, N-dimethylformamide to obtain a polyaniline bilayer hollow sphere.
  • Example 25 Polybutyl acrylate was swelled and polymerized in a shell layer to prepare a polymer composite hollow sphere
  • the octadecyl group contains 0.2% of dodecyl group in water, and is filled with nitrogen.
  • Sodium sulfonate adding 0. 2g of butyl acrylate and 2mg of azobisisobutyronitrile, swelled by magnetic stirring at room temperature for 8 hours, and heated at 80 ° C for 18 hours to obtain a polystyrene-polymethacrylic hollow sphere as a template. , a polymer composite hollow sphere of polybutyl acrylate grown in a shell.

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Abstract

La présente invention concerne des matériaux structurés creux. En particulier, elle concerne la préparation de sphères creuses inorganiques, métalliques ou organiques et des sphères creuses composites utilisant des sphères polymères creuses en tant que modèle. Elle concerne également le procédé pour préparer des sphères creuses présentant des caractéristiques photiques, électriques, magnétiques, catalytiques et leur structure composite. En utilisant des sphères polymères creuses comme modèle, ainsi qu'un procédé sol-gel, une sédimentation, un procédé d'oxydoréduction, les sphères creuses composites ont été préparées par un procédé à interfaces forcées ou un procédé de sédimentation de surface. Les sphères creuses inorganiques, métalliques ou organiques ont été obtenues après élimination du polymère modèle par frittage à température élevée ou extraction sélective par solvant. En contrôlant la réactivité des réactifs, la manière de charger, la concentration des réactifs et le procédé réactif de recyclage, il a été possible de contrôler la structure et de la taille des sphères creuses et de composer simultanément de nombreux matériaux. Les sphères creuses de l'invention présentent non seulement une bonne dispersibilité, mais également une résistance et une stabilité dimensionnelle excellentes. La présente invention concerne également les applications de ces matériaux structurés creux.
PCT/CN2004/001382 2004-11-11 2004-11-30 Procede pour la preparation de spheres creuses et spheres creuses composites avec modele WO2006050638A1 (fr)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19808865A1 (de) * 1998-03-03 1999-09-09 Bayerl Verfahren zur Erzeugung von quervernetzten Strukturen kolloider Dimensionen und definierter Form aus polymerisierbaren Fulleren-(C60)-Derivaten unter Verwendung selbstorganisierter Strukturen aus amphiphilen Molekülen als Template
WO1999047253A1 (fr) * 1998-03-19 1999-09-23 MAX-PLANCK-Gesellschaft zur Förderung der Wissenschaften e.V. Fabrication de particules et de coques creuses enduites multicouches par assemblage automatique de multicouches de nanocomposites sur des gabarits colloidaux decomposables
CN1506308A (zh) * 2002-12-11 2004-06-23 中国石油化工股份有限公司 制备沸石空心微球的方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19808865A1 (de) * 1998-03-03 1999-09-09 Bayerl Verfahren zur Erzeugung von quervernetzten Strukturen kolloider Dimensionen und definierter Form aus polymerisierbaren Fulleren-(C60)-Derivaten unter Verwendung selbstorganisierter Strukturen aus amphiphilen Molekülen als Template
WO1999047253A1 (fr) * 1998-03-19 1999-09-23 MAX-PLANCK-Gesellschaft zur Förderung der Wissenschaften e.V. Fabrication de particules et de coques creuses enduites multicouches par assemblage automatique de multicouches de nanocomposites sur des gabarits colloidaux decomposables
CN1506308A (zh) * 2002-12-11 2004-06-23 中国石油化工股份有限公司 制备沸石空心微球的方法

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
CAIXIA SONG ET AL: "Preparation of Inorganic Hollow Micro-sphere by Templating Against Polymer Colloidal Particles and its Application.", MATERIALS REPORT., vol. 17, no. 7, July 2003 (2003-07-01), pages 32 - 34 *
XUN FU ET AL: "Preparation of CdS Hollow Spheres Using Poly-(styrene-acrylic acid) Latex Particles as Template.", QINGDAO TECHNOLOGY UNIVERSITY TRANSACTION., vol. 25, no. 2, April 2004 (2004-04-01), pages 136 - 138 *

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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